Heavy metals in wastewater

2013/3/22

HEAVY METALS IN WASTEWATER

HEAVY METALS IN WASTEWATER REMOVAL AND ANALYSES

2013/3/22

HEAVY METALS IN WASTEWATER

HEAVY METALS AND THEIR SOURCES

• The most commonly

encountered toxic heavy

metals in wastewater:

• Arsenic, Lead, Mercury, Cadmium

• Less common: Chromium, Copper, Nickel, Zinc

• Sources

• Industrial sources: e.g. Printed board manufacturing, metal finishing and plating, semiconductor manufacturing, textile dyes

• Street runoffs

• Landfills

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HEAVY METALS IN WASTEWATER

PROBLEMS CAUSED BY HEAVY METALS

• Many heavy metals are essential

trace elements for humans,

animals and plants in small

amounts

• In larger amounts cause acute

and chronic toxicity.

• Linked to learning disabilities,

cancers and even death

• Heavy metals have inhibitory

effects on the biological

treatment process at the

wastewater treatment plants

• Limit the use of biosolids as

fertilizer and may inhibit the

digestion process in biogas plant

Kuva:Pasi Valkama

2013/3/22

HEAVY METALS IN WASTEWATER

THE OCCURRENCE OF HEAVY METALS IN NATURE AND WASTEWATERS

• Many heavy metals occur also

naturally

• Contribution from human

activities important for lead,

cadmium and nickel.

• Measurements from the

bottom sediments of the Golf

of Finland suggest that

highest pollution occurred

during 1970-1980, a 40%

decrease in recent sediments

• The heavy metal

concentrations in treatment

plant sludges have decreased

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HEAVY METALS IN WASTEWATER

WAYS OF MINIMIZING THE CONCENTRATIONS OF HEAVY METALS

• Pretreatment of industrial

effluents

• More cost-effective and easier treatment

• Recovery possible

• Agreements for industrial

effluents with fixed limits for

heavy metals

• Control samples from effluents

• Examples of used limits

• Cd < 0,01 mg/l; Ni < 0,5 mg/l

• Pb < 0,5 mg/l; Zn < 3,0 mg/l

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HEAVY METALS IN WASTEWATER

REMOVAL OF HEAVY METALS AT THE MUNICIPAL WASTEWATER TREATMENT PLANT

• Activated sludge process

does not remove most of

the heavy metals

efficiently

• Inhibition at high

concentrations

• More load mainly from the

use of chemicals

• Heavy metals do not

disappear nor react – they

are either in the water or

in the sludge!

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HEAVY METALS IN WASTEWATER

REMOVAL OF HEAVY METALS 1/3

• Chemical precipitation

• Hydroxide precipitation NaOH or Ca (OH)2, pH 8 – 11

• Addition of coagulants possible

• + 99 % removal possible

• - Requires high concentration, produces sludge, some metal hydroxides are amphoteric, inhibition by complexing agents

• Also sulfide precipitation (possible using sulfate-reducing bacteria), chelates

(Rast, 2013)

2013/3/22

HEAVY METALS IN WASTEWATER

REMOVAL OF HEAVY METALS 2/3

• Ion exchange

• High efficiency, fast process

• Synthetic resins are most common

• Research with natural zeolite

• – cost-effective at high concentration, secondary pollution from regeneration

• Adsorption

• Activated carbon – price increasing

• Carbon nanotubes (CNT)

• Low-cost or bioadsorbents (e.g. zeolite, clay; potato peels, eggshell, banana peels etc.)

• Separation of biosorbents still a problem

2013/3/22

HEAVY METALS IN WASTEWATER

REMOVAL OF HEAVY METALS 3/3

• Membrane filtration

• Ultrafiltration, nanofiltration, reverse osmosis

• Micellar enhanced (MEUF) = addition of surfactants to wastewater beyond the critical concentration, recovery and reuse of surfactant?

• polymer enhanced (PEUF), research stage

• NF&RO, high energy cost and membrane restoration

• Flotation

• Ion flotation = imparting the ionic metals hydrophobic an d removal by air bubbles

• Electrochemical methods

• Electrocoagulation (Fe or Al eletrodes)

• Electroflotation (water eletrolysis)

• Eletrodeposition (recovery)

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HEAVY METALS IN WASTEWATER

REACHING VERY LOW LEVELS OF HEAVY METALS IN THE EFFLUENT

• EU priority substances with

environmental quality

standards:

• Mercury < 5 µg/l ; 0,05 µg/l

• Lead ; 7,2 µg/l

• Cadmium < 10 µg/l ; 0,08 – 0,25 µg/l

• Nickel ; 20 µg/l

• Concentrations in Finnish

treated wastewater typically

• Cd < 0,5 µg/l; Hg < 0,2 µg/l

• Pb < 3 µg/l ; Ni < 10 µg/l

2013/3/22

HEAVY METALS IN WASTEWATER

ANALYSING HEAVY METALS IN WASTE WATER

• Waste water samples are

usually digested using

microwave digestion in aqua

regia or strong nitric acid

• Analyses of the elements are

performed using ICP-MS

technique

• Method is based on the SFS-EN

ISO 17294-2 standard

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HEAVY METALS IN WASTEWATER

ICP-MS (INDUCTIVELY COUPLED PLASMA MASS SPECTROMETER)

• The digest solution is nebulized

and sample aerosol is

transported to argon plasma

• High temperature plasma

produce the ions, which are

introduced into the mass

spectrometer

• The mass spectrometer sorts

the ions according to their

mass-to-charge ration and the

ions are quantified with an

electron multiplier detector

2013/3/22

HEAVY METALS IN WASTEWATER

THANK YOU! KIITOS!